Alkylation process



J. B. MIDDLETON I ALKYLATION PROCESS Original Filed D60. 10, 1941 Oct. 19, 1948.

INVENTOR JULIUS B. MIDDLETON Patented Oct. 19, 1948 ALKYLATION raoonss Julius Blake Middleton, New York, N. Y., assignmto Socony-Vacuum Oil Company, Incorporated, New York, N. Y., a corporation of New York Continuation of application Serial No. 422,362,

This application Novemher 5, 1945, Serial No. 626,865

December 10, 1941.

2 Claims...

This invention relates to methods and apparatus for introducing a reactant, or reactants to a chemical process and is particularly concerned with operations of that type wherein the added reactant or reactants are injected into a stream of previously formed reaction mixture.

The apparatus disclosed and the specifichrocess steps described hereinafter as illustrative of the invention are admirably adapted to the requirements of processes for the alkylation of isoparaifins, by reactionwith olefin-s in the presence of a suitable alkylation catalyst such as the acid catalysts, sulphuric, hydrofluoric, etc. The organic reactants and the acid catalyst in such processes are mutually immiscible and because of the rather great difierence in specific gravitiesthey tend to separate. It is, therefore, necessary to provide foradequate agitation of the mass during mixing and throughout the desired time ofcontact'between reactants and catalyst. Further requirements of the process arise from the facility with which the olefin polymerizes in the presence of the catalyst, thus reducing the yield available. The latter problem is commonly overcome in large measure by conducting the reaction in the presence of a very large excess of iso-paraffins to promote the alkylation reactionandsuppress polymerization. Both these desired conditionsare advantageously achieved to ,a substantial extent. by use of a reactor of large; volume from which .a-portion of the reactionmass is withdrawn. for'separation of product and another portion drawn off and passed through a circuit external to the reactor. Fresh catalyst and reactants are added to the strea in. the external circuit and the resultantmixture of catalyst, reactants, reaction products and reactioniby-products is then returned to the re actor. Theagitation provided by recirculated reaction mixture aids materially in promoting ade- 1 quate contactand the excess of paraffin hydrocarbon which. accumulatesin the reaction mix ture provides .a reaction medium for fresh reactants having a very high ratio of paraffin to olefin at the time the olefinfirst contactsthe-cataly st.

'It" should be noted thatthe term reactor'as used hereinapplies to anenclosed space wherein the reaction is largely conducted. It is undoubtedly true that reaction occurs to a substantial extent in parts of the apparatus not included within the reactor, and use of the term is not to be understood as excluding reaction in the external circuit.

Results are far from ideal, however, and attempts have been made to improve the condia tions of the reaction by increasing the ratio, of parafiin to olefin at various points in the circuit where reaction occurs. Many of the previously suggested expedients to this end are valuable aids in the process and utilization of such as may be of help is contemplated in commercial embodiments of the invention. The present -i-nven-, tion contemplates. obtaining superior results in processes of the present. type by utilizing a novel concept of mixing fresh reactants with the emulsion in the external circuit. According to the present invention, a cyclic circulation of reaction mixture is established in a mixer external to the reactor and the fresh reactants are added to the fluids so circulated in saidmixer. The in. ventio provides means and process steps-whereby a more thorough mixing is accomplished and, even more important, the. reaction of fresh iced material is caused to take place in an environ ment having an extremely h h ratio of paraffin to olefin, whereby a high yield .of good quality alkylate is. obtained.

In principle, thev invention. contemplates, the provision of a'body of fluid moving within ami r and injection ,of fresh iced into the said body while continuously adding fresh fluid of similar composition thereto and withdrawing the artially reacted mixture therefrom.

Further objects and advantages of the invention will zbe apparent from discussion of a preferred embodiment thereof, apparatus therefor being shown in the annexed drawings; wherein Figure 1 is a diagrammatic-showing o an a kyl ation uni-t embodying the principles .of the invention;

Figure 12 is an enlarged View in p rti l section of the mixing. device ofthe unitshown in Figure 1;

Figure 3 is an elevation of the means for ad.- mitting fresh feed to the chamber of the mixing device; and

Figure .4 is. an elevation of the injector for recirculated emulsion.

Refer pecifically o Figure 1, the unit for catalytic alkylation,;such as the reaction between iso-butane and butane in the presence of a mineral acid, includes a reactor i=0 having a dis charge line H -f or removing emulsion from the r a tion -,m s wit in said reactor. Fr sh acid catalyst is add d to he emulsion through-line l2 and the mixture is then passed through a pump I3 which mixes the mass and propels it to mixer l4. Fresh feed in the form of a mixture of iso-butane and butene in the ratio of between 6 and 7 to 1 is supplied to mixer I4 from pipe IS. The mass resulting from mixing of fresh feed with recirculated emulsion is withdrawn from the mixer l4 and passed through line I B to the reactor ID. A further portion of the reaction mass is withdrawn from reactor Hi through discharge I 1', preferably'continuously, and passed to apparatus for separation of product and unreacted material from spent acid catalyst. It is to be understood, of course, that the illustrated unit is capable of extensive modifica tion in connection with cooling apparatus, recycling of acid and/or hydrocarbons separated from the mixture withdrawn through line I! and numerous other respects. This invention is concerned primarily with the mixing device and the process practiced therein, wherefore only ele ments of the system essential'to an understand ing of the operation of the mixer and its function in a complete plant have been illustrated.

The mixer comprises a shell defining the mixing zone together with means for adding the materials to be mixed and means for withdrawing the mixture preparedin' the mixer. Emulsion withdrawn from the reactor and having acid catalyst admixed therewith enters the mixer through pipe 18, while the fresh feed stock is introduced to the mixer through pipe 19. The mixture from pipe I8 passes through a distributing head and enters the actual mixing zone asa plurality of fine streams issuing from a number of small orifices 24 in the face of the head 20. Fresh feed entering through pipe 19 passes to the interior of a rotatable hollow impeller 2! having a plurality of radial vanes or blades 22 each pitched so that the assembly has a propeller effect when rotated about its axis. Each of the blades has a line of small orifices 23 disposed as shown and communicating with the interior of the impeller 2|, in order that fluid under-pres sure admitted through pipe 15 will pass out through said orifices and impart a turning moment by a reaction effect to the impeller 2! tending to turn it in a direction to cause flow of fluid longitudinally of the mixer andthrough the midregion thereof toward the distributing head 20.

The pipe [9 is mounted for rotation about its axis in the end wall of the shell of mixer M by' means of apacking gland indicated generally at 25. A fluid-tight rotatable connection 26 is made between pipes l9 and I5.- I

While the reaction effect of the fluid issuing from orifices 23 will often suffice to cause rotation of impeller 2| at a feasible rate, it isdesirable in some cases to provide auxiliary or supplemental means for rotating the impeller assembly. This purpose may be served advantageously by a bevel gear 21 keyed to the pipe l9 and meshing with a bevel gear on a shaft 28 driven from a suitable source of power not shown.

It will be apparent that in operation'the impeller turns in a directionto cause a vigorous circulation of fluids in the mixing chamber in the manner indicated by the fiow lines in Figure 2.

The stream flowing past each blade 221s composed of acid catalyst, butene and isobutane with the latter heavily predominant, and products of the reaction. Each small stream issuing" from an orifice 23 contains butene in relatively small quantities and is immediately further diluted as regards the butene content as it contacts acid then caused to pass toward the outer portion of the mixing zone around to the rear of the impeller 2!. A portion of the mass so circulated is withdrawn from the mixer and passed to the reactor as partially reacted reaction mass, while the remainder again passes through the blades of the impeller 2! to repeat the cycle. It will be recognized by those skilled in the art that coolers, valves and other accessories are desirable for operations at high efliciency, but these constitute no part of the invention and, since they must vary with changes in design of various elements of a complete plant and with the specific nature and amounts of materials fed to the system, are not illustrated here.

This application is a continuation of my copending application Serial No. 422,362, filed December 10, 1941,

I claim:

1. A process for the catalytic alkylation of an alkylatable hydrocarbon with an alkylating agent in the presence of a liquid alkylation catalyst which comprises introducing the alkylatable hydrocarbon and the liquid alkylation catalyst into a reaction zone, maintaining a relatively large body of liquid reaction mixture under alkylating conditions in said zone, agitating said body of reaction mixture, introducing the alkylating agent into said body of reaction mixture through an orifice, and throughout said introduction movin said orifice at high speed through the body of reaction mixture in said zone and thereby effecting rapid dispersal of said alkylating agent throughout said body of reaction mixture, preventing local concentrations of the alkylating agent in said body and maintaining the concentration of the alkylating agent throughout the reaction zone at the desired minimum.

2. A process for the catalytic alkylation of an alkylatable hydrocarbon with an alkylating agent in the presence of a liquid alkylation catalyst through the body of reaction mixture in said zone and thereby efiecting rapid dispersal of said alkylating agent throughout said body of reaction mixture, preventing local concentrations of the alkylatin agent in said body and maintaining the concentration of the alkylating agent throughout the reaction zone at the desired minimum.

JULIUS BLAKE MIDDLETON.

No references cited. 

